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Ceramic, Cermet, Or Metal Powder Materials with a Polymeric Binder, and Process for Producing Formed Shapes of Ceramic, Cermets, Or Metal Powders

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Ceramic, Cermet, Or Metal Powder Materials with a Polymeric Binder, and Process for Producing Formed Shapes of Ceramic, Cermets, Or Metal Powders Europaisches Patentamt 244 940 J European Patent Office Publication number: 0 A2 Office europeen des brevets EUROPEAN PATENT APPLICATION C 04 B B 22 C 1/20, Application number: 87302698.3 ® mtci/: 35/00, B22F 1/00 Date of filing: 27.03.87 Dow Priority: 31.03.86 US 846407 Applicant: THE DOW CHEMICAL COMPANY, 2030 Center Abbott Road P.O. Box 1967, Midland, Ml 48640 (US) Date of publication of application: 11.11.87 Inventor: Schuetz, James E., 1512 Crane Court, Midland Bulletin 87/46 Michigan 48640 (US) Representative: Raynor, John et al, W.H. Beck, Greener & Co 7 Stone Buildings Lincoln's Inn, London WC2A 3SZ Designated Contracting States: BE DE FR GB IT NL SE (GB) @ Ceramic, cermet, or metal powder materials with a polymeric binder, and process for producing formed shapes of ceramic, cermets, or metal powders. © A composition is disclosed comprising a ceramic, cer- met or metal powder material and, as a binder, poly(ethyl- oxazoline). A process for preparing the composition is provided. CM < O 0) CM o Q. Ill ACTORUM AG 0 244 940 -1- MODIFIED TITLE see front page NOVEL CERAMIC, CERMET OR METAL POWDER BINDER AND PROCESS THEREFOR This invention concerns generally a ceramic, cermet or metal powder composition and a process for said j. producing composition. Conventional ceramic, cermet or metal powder processing typically comprises ball milling a slurry, which contains a ceramic, cermet or metal powder material and a solvent, to reduce the particle size of the material. The milled slurry is dried, such as by spray drying or pan drying, and the dried composition is then formed into articles. In the fabrication of ceramic, cermet or metal powder articles, a binder may be employed. A good binder must satisfy several criteria. It should be soluble in the slurry containing the ceramic, cermet or metal powder and it should have a low solution 20 viscosity thereby permitting high solids content in the slurry and facilitating ball milling. Also, a good binder should be compatible with other additives and processing steps. Since the binder is not a desirable 25 component of a final article, it should be easily 0 244 940 -2- removable at some point in the processing sequence. In addition, the binder should impart green strength to the green fabricated article. 5 Surprisingly, it has now been found by this invention that a suitable binder is poly- (ethyloxazoline) for use in a ceramic, cermet or powder composition. Another 10 aspect of this invention is a process comprising forming a slurry containing a ceramic, cermet or powder material and poly(ethyloxazoline) , converting said slurry into a substantially dry powder, and converting the powder into a ceramic, cermet or 15 metal powder body of a desired shape. A further aspect of this invention is a ceramic, cermet or metal powder body prepared by the process comprising forming a slurry containing the 20 material and poly ( e thy loxazo line) , converting said slurry to a substantially dry powder, and converting the powder into a ceramic, cermet or metal powder body of a desired shape. 25 In general, any ceramic composition which comprises an inorganic, nonmetallic material as its essential component can be employed in this invention. Minor impurities can be present in the ceramic material so long as they do not substantially affect the densification of said material. Preferably, the ceramic material consists essentially of a ceramic and, more preferably, the ceramic material consists of a ceramic. Preferred ceramics include, for example, oxides, ^g carbides, nitrides, silicides, borides, phosphides, sulfides and mixtures thereof. More 34,743-F -2- 0 244 940 -3- preferred ceramics include magnesia, mullite, thoria, beryllia, urania, spinels, zirconium oxide, bismuth oxide, aluminum oxide, magnesium oxide, barium titanate, corderite, boron nitride, tungsten carbide, 5 tantalum carbide, titanium carbide, niobium carbide, zirconium carbide, boron carbide, hafnium carbide, silicon carbide, niobium boron carbide, aluminum nitride, titanium nitride, zirconium nitride, tantalum nitride, hafnium nitride, niobium nitride, boron 10 nitride, silicon nitride, titanium boride, chromium boride, zirconium boride, tantalum boride, molybdenum boride, tungsten boride, cerium sulfide, molybdenum sulfide, cadmium sulfide, zinc sulfide, titanium sulfide, magnesium sulfide, zirconium sulfide and mixtures and alloys of these. Even more preferred ceramics include zirconium oxide, aluminum oxide, magnesium oxide, barium titanate, silicon carbide, corderite, spinels and boron nitride. The most 20 preferred ceramic is aluminum oxide. Also, any cermet composition which comprises at least one inorganic, metallic material as one of its components can be employed in this invention. Minor 25 impurities can be present in the cermet material so long as they do not substantially affect the densification of said material. Preferred cermets include, for example, oxides, carbides, nitrides, silicides, borides, sulfides or mixtures thereof. More 3° preferred cermet materials include alumina, zirconia, magnesia, mullite, zircon, thoria, beryllia, urania, spinels, tungsten carbide, tantalum carbide, titanium carbide, niobium carbide, zirconium carbide, boron carbide, niobium __ carbide, hafnium carbide ,._sil.icon boron carbide, aluminum nitride, titanium nitride, 3M,743-F -3- 0 244 940 -4- zirconium nitride, tantalum nitride, hafnium nitride, niobium nitride, boron nitride, silicon nitride, titanium boride, chromium boride, zirconium boride, tantalum boride, molybdenum boride, tungsten boride, 5 cerium sulfide, molybdenum sulfide, cadmium sulfide, zinc sulfide, titanium sulfide, magnesium sulfide, zirconium sulfide or mixtures thereof. Even more preferred cermet materials include tungsten carbide, niobium carbide, titanium carbide, silicon carbide, niobium boron carbide, tantalum carbide, boron carbide, alumina, silicon nitride, boron nitride, titanium nitride, titanium boride or mixtures thereof. Even more preferred cermet materials are tungsten carbide, niobium carbide .J5 and titanium carbide. The most preferred cermet material is tungsten carbide. Furthermore, any metal powder composition which comprises a metallic material or mixtures of metallic materials 20 as its essential component can be employed in this invention. Minor impurities can be present so long as they do not substantially adversely affect the properties of the final material, preferred metal powders include, for example, alumina, zirconia, 25 magnesia, thoria, beryllia, tungsten, tantalum, titanium, niobium, boron, hafnium, silicon, aluminum, zirconium, chromium, molybdenum, cerium, cadmium, zinc, magnesium, cobalt, nickel, iron, vanadium, palladium, copper or alloys thereof or mixtures thereof. 30 In a preferred embodiment of this invention, the ceramic, cermet or metal powder material is particulate and has a particle size of about 100 microns or less, more preferably about 10 microns or less, and most preferably about 1 micron or less. In another preferred embodiment, fibrous ceramic material 34,743-F -4- 0 244 940 -5- or other reinforcing ceramic material can be mixed with the particulate ceramic material. It is believed that incorporation of fibrous ceramic material or other reinforcing ceramic material may increase the strength 5 and fracture toughness of the ceramic body produced. The binder, poly(ethyloxazoline) , is employed" in a binding amount. Preferably, the binder is employed in an amount sufficient to provide a green 10 ceramic article with enough strength to retain its shape during normal handling and processing. Preferably the ceramic composition comprises between 0.1 and 20 weight percent poly(ethyloxazoline) and more preferably between 0.1 and 10 weight percent based on 1^ the weight of the ceramic material. Even more preferably, said composition comprises between 0.2 and 5 weight percent of poly(ethyloxazoline) , and most preferably from 0.5 to 3.0 weight percent. The poly(ethyloxazoline) preferably has a weight average 20 molecular weight ranging from 10,000 to 750,000 and more preferably from 50,000 to 500,000. In a preferred embodiment of this invention, the consists of a ceramic, cermet or metal pc composition powder and poly(ethyloxazoline) , and more preferably the composition consists of a ceramic and poly- (ethyloxazoline) . An optional component of the composition of this invention is a metallic material of cobalt, nickel, iron, tungsten, molybdenum, tantalum, titanium, chromium, niobium, boron, zirconium, vanadium, silicon, palladium, hafnium, aluminum, copper and alloys and 35 mixtures thereof. 3M,7*»3-F -5- 0 244 940 -6- The process of this invention comprises forming a slurry of the material and poly(ethyloxazoline) . The slurry preferably contains a solvent which substantially solubilizes poly(ethyloxazoline) . 5 Preferred solvents include polar organic solvents such as water, methanol, ethanol, acetone, and mixtures thereof. Water is the most preferred solvent due to its ease of use and nonflammability. -However., solvents such as methanol, ethanol and acetone are particularly useful in this invention due to the chemical reactions that may occur if the ceramic is in the presence of water. For example, nitrides may form oxides in the presence of water, and this may or may not be desired. In 15 a preferred embodiment of this invention, the slurry, comprising particulate ceramic, cermet or metal powder material and poly(ethyloxazoline), is ball milled by conventional and well-known techniques. The ball milling reduces the
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